US9487883B2 - Trimanganese tetraoxide and its production process - Google Patents
Trimanganese tetraoxide and its production process Download PDFInfo
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- US9487883B2 US9487883B2 US14/395,191 US201314395191A US9487883B2 US 9487883 B2 US9487883 B2 US 9487883B2 US 201314395191 A US201314395191 A US 201314395191A US 9487883 B2 US9487883 B2 US 9487883B2
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- trimanganese tetraoxide
- particles
- manganese
- aqueous solution
- pores
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- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 title claims abstract description 228
- KVGMATYUUPJFQL-UHFFFAOYSA-N manganese(2+) oxygen(2-) Chemical compound [O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++] KVGMATYUUPJFQL-UHFFFAOYSA-N 0.000 title claims abstract description 173
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- 239000002245 particle Substances 0.000 claims abstract description 158
- 239000011148 porous material Substances 0.000 claims abstract description 107
- 239000007864 aqueous solution Substances 0.000 claims abstract description 87
- 150000002696 manganese Chemical class 0.000 claims abstract description 42
- 239000011164 primary particle Substances 0.000 claims abstract description 39
- 239000003513 alkali Substances 0.000 claims abstract description 28
- 239000002002 slurry Substances 0.000 claims abstract description 28
- 239000007787 solid Substances 0.000 claims abstract description 20
- 230000033116 oxidation-reduction process Effects 0.000 claims abstract description 19
- 150000002642 lithium compounds Chemical class 0.000 claims abstract description 18
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 35
- 238000002156 mixing Methods 0.000 claims description 31
- 238000002425 crystallisation Methods 0.000 claims description 13
- 230000008025 crystallization Effects 0.000 claims description 13
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 8
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 8
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 8
- 229910052753 mercury Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 43
- 239000011572 manganese Substances 0.000 abstract description 43
- 229910052748 manganese Inorganic materials 0.000 abstract description 42
- 239000000463 material Substances 0.000 abstract description 21
- 229910002102 lithium manganese oxide Inorganic materials 0.000 abstract description 16
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 abstract description 16
- 230000009257 reactivity Effects 0.000 abstract description 9
- 239000013078 crystal Substances 0.000 description 19
- 238000002441 X-ray diffraction Methods 0.000 description 15
- 238000005259 measurement Methods 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000009826 distribution Methods 0.000 description 11
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 9
- 239000012066 reaction slurry Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 229910016978 MnOx Inorganic materials 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 6
- 229910001437 manganese ion Inorganic materials 0.000 description 6
- 229940099596 manganese sulfate Drugs 0.000 description 6
- 239000011702 manganese sulphate Substances 0.000 description 6
- 235000007079 manganese sulphate Nutrition 0.000 description 6
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000011163 secondary particle Substances 0.000 description 6
- 229910052596 spinel Inorganic materials 0.000 description 6
- 239000011029 spinel Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000005054 agglomeration Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000008139 complexing agent Substances 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 239000006182 cathode active material Substances 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- -1 cobalt oxyhydroxide Chemical compound 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002993 LiMnO2 Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910006130 SO4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- VGYDTVNNDKLMHX-UHFFFAOYSA-N lithium;manganese;nickel;oxocobalt Chemical compound [Li].[Mn].[Ni].[Co]=O VGYDTVNNDKLMHX-UHFFFAOYSA-N 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/12—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by electrolysis
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- C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
-
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- C30B30/00—Production of single crystals or homogeneous polycrystalline material with defined structure characterised by the action of electric or magnetic fields, wave energy or other specific physical conditions
- C30B30/02—Production of single crystals or homogeneous polycrystalline material with defined structure characterised by the action of electric or magnetic fields, wave energy or other specific physical conditions using electric fields, e.g. electrolysis
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- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
Definitions
- the present invention relates to trimanganese tetraoxide suitable as a manganese material of a cathode active material of a lithium ion secondary battery, and its production process.
- a lithium manganese oxide is used as a cathode active material for a lithium ion secondary battery.
- electrolytic manganese dioxide is widely used.
- trimanganese tetraoxide is also used as a preferred manganese material of a lithium manganese oxide, whereby the fillability of the obtained lithium manganese oxide tends to improve (for example, Patent Documents 1 and 2).
- Trimanganese tetraoxide is converted to a lithium manganese oxide by being mixed with a lithium material and another metal material, followed by firing.
- a lithium manganese oxide obtained by mixing and grinding lithium hydroxide and trimanganese tetraoxide, followed by firing, has been reported (Patent Document 1).
- a lithium nickel manganese cobalt oxide obtained by forming lithium carbonate, trimanganese tetraoxide, cobalt oxyhydroxide, nickel hydroxide and the like into a slurry, and wet grinding the slurry, followed by firing, has been reported (Patent Document 2).
- trimanganese tetraoxide to be a manganese material of a lithium manganese oxide for the purpose of uniform mixing, trimanganese tetraoxide having a maximum particle size of at most 150 nm, obtained by mixing a manganese-containing liquid with an alkali liquid, followed by oxidation, has been reported (Patent Document 3). Further, trimanganese tetraoxide having a large average primary particle size of from 3.0 to 15 ⁇ m and having a low Na content and a low S content, in order to obtain lithium manganate particle powder having a large primary particle size and having a small amount of agglomerated particles, has been reported (Patent Document 4).
- Patent Document 1 JP-A-2003-086180
- Patent Document 2 JP-A-2012-023015
- Patent Document 3 JP-A-2001-261343
- Patent Document 4 JP-A-2004-292264
- the trimanganese tetraoxide in Patent Document 3 has a very small average particle size of at most 100 nm and has a high dispersibility. Accordingly, it has a relatively high reactivity with a lithium compound, but has a poor flowability and is hardly industrially handled.
- the trimanganese tetraoxide in Patent Document 4 has a large primary particle size and thus is excellent in the dispersibility. However, since it comprises large primary particles, it has a low reactivity with a lithium compound, and the battery performances particularly the output characteristics of a lithium manganese oxide obtained from it as a material are not sufficient.
- the object of the present invention is to solve such problems and to provide trimanganese tetraoxide suitable as a manganese material of a lithium manganese oxide and its production process.
- trimanganese tetraoxide used as a material of a lithium manganese oxide and its production process.
- trimanganese tetraoxide particles comprising secondary particles having primary particles agglomerated with an appropriate strength can be a manganese material of a lithium manganese oxide with excellent handleability, without a decrease of a reactivity with a lithium compound.
- the present invention provides the following.
- the trimanganese tetraoxide particles which have an appropriate strength since primary particles are present even in their interior, and which are easily ground.
- the trimanganese tetraoxide particles are easily handled e.g. in a transport step, and by grinding the particles at the time of mixing, the primary particles are dispersed, and the reactivity with a lithium compound or the like will not be lowered.
- the trimanganese tetraoxide particles are excellent in the handleability and can be a manganese material of a lithium manganese oxide which is easily handled industrially.
- the trimanganese tetraoxide particles of the present invention homogeneously have pores even in the interior of the particles, removal of the impurities is easy.
- trimanganese tetraoxide particles can easily and continuously be produced.
- FIG. 1 illustrates a particle size distribution of trimanganese tetraoxide particles in Example 1.
- FIG. 2 is a SEM photograph of trimanganese tetraoxide particles in Example 1 (scale: 10 ⁇ m)
- FIG. 3 is a SEM photograph of the surface of trimanganese tetraoxide particles in Example 3 (scale: 1 ⁇ m)
- FIG. 4 is a SEM photograph of a cross section of trimanganese tetraoxide particles in Example 3 (scale: 1 ⁇ m)
- trimanganese tetraoxide particles of the present invention will be described.
- the trimanganese tetraoxide particles of the present invention comprise particles having trimanganese tetraoxide having an average primary particle size of at most 2 ⁇ m agglomerated, that is, secondary particles having trimanganese tetraoxide primary particles having an average particle size of at most 2 ⁇ m agglomerated.
- the average primary particle size is preferably at most 1 ⁇ m, more preferably at most 0.5 ⁇ m, further preferably at most 0.45 ⁇ m, still further preferably at most 0.4 ⁇ m. By the average primary particle size being at most 2 ⁇ m, the reactivity with a lithium compound tends to be high.
- the average primary particle size i.e. the average particle size of the trimanganese tetraoxide primary particles is preferably at least 0.1 ⁇ m, more preferably larger than 0.2 ⁇ m.
- the trimanganese tetraoxide particles of the present invention are particles having trimanganese tetraoxide having an average primary particle size of at most 2 ⁇ m agglomerated.
- the trimanganese tetraoxide particles of the present invention are particles having trimanganese tetraoxide having an average primary particle size of at most 2 ⁇ m agglomerated.
- the flowability of a powder tends to be high, whereby the handleability before the mixing step tends to improve.
- the primary particles constituting the trimanganese tetraoxide particles of the present invention are dispersed, and mixing with a lithium compound and the like is possible while maintaining the high reactivity with them.
- primary particles are particles of minimum unit which can be confirmed as separate particles by scanning electron microscope observation.
- the trimanganese tetraoxide particles of the present invention form pores by agglomeration of the primary particles.
- the pore volume of the pores is at least 0.4 mL/g, preferably at least 0.5 mL/g, more preferably at least 0.7 mL/g, whereby the trimanganese tetraoxide particles of the present invention are easily ground. If the pore volume of the pores is less than 0.4 mL/g, agglomeration of the primary particles tends to be too strong, and the trimanganese tetraoxide particles are hardly ground.
- the pore volume of the pores of the trimanganese tetraoxide particles of the present invention tends to be at most 2 mL/g, further at most 1.5 mL/g, still further at most 1 mL/g.
- trimanganese tetraoxide particles of the present invention are particles excellent in the handleability and the grinding property only if both of the average primary particle size and the pore volume are satisfied.
- the shape of the trimanganese tetraoxide particles of the present invention is a sphere, preferably a sphere having pores on its surface.
- a sphere means a sphere having an acute angle portion or a sphere not in the form of a polyhedron, and it includes not only a true sphere but also a distorted sphere such as an approximate sphere, or such a sphere having pores on its surface.
- the most frequent pores are preferably pores having a diameter of at most 5 ⁇ m, more preferably pores having a diameter of at most 4 ⁇ m, further preferably pores having a diameter of at most 3 ⁇ m.
- the most frequent pores are pores with a largest volume among pores which the trimanganese tetraoxide particles of the present invention have.
- the trimanganese tetraoxide particles of the present invention have a pore structure such that the primary particles are present even in their interior and the pores are uniformly dispersed in the particles, not a pore structure of a so-called hollow sphere such as a table tennis ball.
- the trimanganese tetraoxide particles of the present invention have an appropriate strength even though they are easily ground.
- the most frequent pores are preferably pores having a diameter of at least 1 ⁇ m, more preferably pores having a diameter of at least 2 ⁇ m.
- the trimanganese tetraoxide particles of the present invention have a pore volume ratio of pores having a diameter of at least 10 ⁇ m as measured by a mercury intrusion technique (hereinafter referred to simply as “a pore volume ratio of pores having a diameter of at least 10 ⁇ m”) of preferably at most 20%, more preferably at most 15%, further preferably at most 10%.
- a pore volume ratio of pores having a diameter of at least 10 ⁇ m By the pore volume ratio of pores having a diameter of at least 10 ⁇ m being at most 20%, the reactivity with a lithium compound tends to be uniform.
- the pore volume ratio is a ratio of the total volume of pores having a diameter within a predetermined range (for example, pores having a pore diameter of at least 10 ⁇ m) to the total volume of all the pores of the trimanganese tetraoxide particles.
- the diameter distribution and the pore volume of pores can be measured by a commercially available porosimeter employing a mercury intrusion technique.
- the trimanganese tetraoxide particles of the present invention have a pore area ratio of pores having a diameter of at most 0.1 ⁇ m as measured by a mercury intrusion technique (hereinafter referred to simply as “a pore area ratio of pores having a diameter of at most 0.1 ⁇ m”) of preferably at least 1.5%, more preferably at least 5%.
- a pore area ratio of pores having a diameter of at most 0.1 ⁇ m preferably at least 1.5%, more preferably at least 5%.
- the pore area ratio in the present invention is a ratio of the total area of pores having a diameter within a predetermined range (for examples, pores having a pore diameter of at most 0.1 ⁇ m) to the total area of all the pores of the trimanganese tetraoxide.
- the diameter distribution and the pore area of pores may be measured by a commercially available porosimeter employing a mercury intrusion technique.
- the BET specific surface area of the trimanganese tetraoxide particles of the present invention is optional so long as the particles have the above pore volume.
- the BET specific surface area of the trimanganese tetraoxide particles of the present invention may be at least 2 m 2 /g, further at least 3 m 2 /g, still further at least 5m 2 /g.
- trimanganese tetraoxide particles of the present invention are ground when mixed with a lithium compound. Accordingly, the fillability as the trimanganese tetraoxide particles is not particularly limited, however, the tap density may, for example, be less than 1.5 g/cm 3 , further at most 1.4 g/cm 3 .
- the particle size distribution may not be monomodal, and the modal particle size and the average particle size may be different from each other.
- the modal particle size is a particle size with the highest frequency.
- the modal particle size tends to be larger than the average particle size (that is, the modal particle size>the average particle size). Accordingly, the modal particle size may be at least 1.05 times the average particle size (that is, the modal particle size/the average particle size ⁇ 1.05), further at least 1.1 times (that is, the modal particle size/the average particle size ⁇ 1.1), further at least 1.3 times (that is, the modal particle size/the average particle size ⁇ 1.3).
- the specific modal particle size may be at least 6 ⁇ m, further at least 9 ⁇ m, particularly at least 11 ⁇ m.
- the tap density in the present invention is an apparent density of a powder obtained by tapping a container under specific conditions. Accordingly, it is different from a so-called press density i.e. a density of a powder in a state where the powder is packed in a container and pressure-molded under a certain pressure.
- the tap density may be measured, for example, by a method disclosed in the after-mentioned Examples.
- the particle size of the trimanganese tetraoxide particles of the present invention is optional so long as the particles have the above pore volume.
- the average particle size of the trimanganese tetraoxide particles of the present invention may be at least 5 ⁇ m, preferably at least 10 ⁇ m.
- the upper limit of the average particle size may be at most 50 ⁇ m, further at most 20 ⁇ m.
- the average particle size of the trimanganese tetraoxide particles of the present invention means an average particle size of secondary particles having trimanganese tetraoxide having an average primary particle size of at most 2 ⁇ m agglomerated.
- the average particle sizes of the primary particles and the secondary particles are both volume average particle sizes.
- trimanganese tetraoxide The chemical formula of trimanganese tetraoxide is represented as Mn 3 O 4 . Accordingly, in a case where trimanganese tetraoxide is represented by MnO x , the ratio x of the oxygen element to the manganese element is from 1.33 to 1.34. However, the ratio x of oxygen to manganese of trimanganese tetraoxide constituting the trimanganese tetraoxide particles of the present invention is not limited to 1.33 to 1.34.
- the trimanganese tetraoxide of the present invention has the above crystal structure, and may be a manganese oxide represented by MnO x wherein x is within a range of from 1.20 to 1.40. x is preferably from 1.25 to 1.40, more preferably from 1.30 to 1.40.
- the trimanganese tetraoxide particles of the present invention have a Ca content of preferably at most 100 wtppm, more preferably at most 60 wtppm, particularly preferably at most 30 wtppm.
- the Ca content is preferably lower.
- the trimanganese tetraoxide particles contain 5 wtppm of Ca, there is substantially no influence when used as a material for a lithium manganese oxide.
- the trimanganese tetraoxide particles of the present invention have a Mg content of preferably at most 50 wtppm, particularly preferably at most 20 wtppm. Further, the Mg content is preferably lower. However, even if the trimanganese tetraoxide particles contain 1 wtppm of Mg, there is substantially no influence when used as a material for a lithium manganese oxide.
- the trimanganese tetraoxide particles of the present invention preferably have a low content of sulfate ions (SO 4 2 ⁇ ) as impurities.
- the content of sulfate ions in the manganese oxide is preferably at most 1 wt %, more preferably at most 0.5 wt %, further preferably at most 0.3 wt %.
- the present invention provides a process for producing trimanganese tetraoxide particles comprising a crystallization step of directly crystallizing trimanganese tetraoxide from a manganese salt aqueous solution.
- “Directly crystallizing trimanganese tetraoxide” means that trimanganese tetraoxide is obtained not by means of manganese hydroxide from a manganese salt aqueous solution.
- Such includes an embodiment such that a crystal phase of manganese hydroxide does not form at all from the manganese salt aqueous solution and an embodiment such that fine crystals of manganese hydroxide are precipitated in a short time and then they are converted to trimanganese tetraoxide before they grow into hexagonal plate-form crystals.
- the crystallization step of the present invention does not have a step of precipitating manganese hydroxide crystals from a manganese salt aqueous solution and oxidizing them by an oxidizing agent.
- trimanganese tetraoxide is directly precipitated from the manganese aqueous solution means that hexagonal plate-form crystals of manganese hydroxide do not form from the manganese aqueous solution, and such includes an embodiment such that a crystal phase of manganese hydroxide do not form at all and an embodiment such that fine crystals of manganese hydroxide are precipitated in a short time and they are converted to trimanganese tetraoxide before they grow into hexagonal plate-form crystals.
- a conventional production process comprises a step of forming manganese hydroxide from a manganese aqueous solution in a reducing atmosphere first and then a step of oxidizing it in an oxidizing atmosphere such as in oxygen or in the air to form trimanganese tetraoxide.
- an oxidizing atmosphere such as in oxygen or in the air
- trimanganese tetraoxide it is necessary to change the reaction atmosphere in the middle of the step to obtain trimanganese tetraoxide.
- trimanganese tetraoxide cannot be continuously produced, or the production process tends to be complicated.
- trimanganese tetraoxide is directly crystallized from the manganese salt aqueous solution by producing trimanganese tetraoxide with the above oxidation-reduction potential and manganese molar ratio. Accordingly, in the production process of the present invention, it is not necessary to change the atmosphere in the middle of the step. As mentioned above, in the production process of the present invention, it is not necessary to change the atmosphere during production, and thus trimanganese tetraoxide particles can be continuously produced by mixing a manganese salt aqueous solution with an alkali aqueous solution.
- the manganese salt aqueous solution used in the production process of the present invention may be an aqueous solution containing manganese ions, and may, for example, be an aqueous solution of manganese sulfate, manganese chloride, manganese nitrate, manganese acetate or the like, or a solution having metal manganese, manganese oxide or the like dissolved in an acid aqueous solution of e.g. sulfuric acid, hydrochloric acid, nitric acid or acetic acid.
- an acid aqueous solution e.g. sulfuric acid, hydrochloric acid, nitric acid or acetic acid.
- the manganese ion concentration of the manganese salt aqueous solution may be an optional concentration, and for example, the manganese ion concentration is preferably at least 0.1 mol/L.
- the manganese ion concentration of the manganese salt aqueous solution being at least 0.1 mol/L, the trimanganese tetraoxide particles will efficiently be obtained.
- the temperature of the manganese salt aqueous solution is preferably at least 40° C., more preferably at least 60° C. and at most 95° C., further preferably at least 70° C. and at most 80° C.
- the alkali aqueous solution used in the production process of the present invention may be an aqueous solution showing alkalinity, and may, for example, be an aqueous solution of e.g. sodium hydroxide or potassium hydroxide.
- the concentration of the alkali aqueous solution is not limited, and is optional in relation to the concentration of the manganese salt aqueous solution to achieve the manganese molar ratio of the present invention.
- the concentration of hydroxide ions (OH ⁇ ) of the alkali aqueous solution may, for example, be at least 0.1 mol/L, further at least 0.2 mol/L.
- the oxidation-reduction potential being high, a trimanganese tetraoxide single phase is readily obtained, and when it is at most 300 mV, further at most 200 mV, single phase trimanganese tetraoxide is more readily obtained.
- the oxidation-reduction potential may be obtained as a value to the standard hydrogen electrode (SHE).
- the manganese salt aqueous solution is mixed with the alkali aqueous solution so that the manganese molar ratio is at most 0.55. If the manganese molar ratio exceeds 0.55, a single phase of trimanganese tetraoxide is hardly obtained.
- the manganese molar ratio is preferably at most 0.52, more preferably at most 0.5.
- the manganese molar ratio is at least 0.35, preferably at least 0.4, more preferably at least 0.45, whereby the trimanganese tetraoxide particles will efficiently be produced.
- trimanganese tetraoxide is crystallized and a slurry containing the trimanganese tetraoxide is obtained.
- the solid content concentration of the slurry is at most 2 wt %, preferably at most 1.5 wt %, more preferably at most 1 wt %.
- the lower limit of the solid content concentration of the slurry may, for example, be at least 0.1 wt % as the solid content concentration.
- the solid content concentration means the concentration of trimanganese tetraoxide in the slurry.
- the solid content concentration of the slurry is preferably within the above range and constant.
- the obtained trimanganese tetraoxide particles are likely to be homogeneously ground.
- a method of adjusting the solid content concentration of the slurry to be constant a method of withdrawing a part of the slurry simultaneously with mixing of the manganese salt aqueous solution with the alkali aqueous solution may, for example, be mentioned.
- trimanganese tetraoxide is aged in the slurry, whereby agglomeration of the primary particles is accelerated, and trimanganese tetraoxide particles having an appropriate size are likely to be obtained.
- the ageing time is preferably at least 10 minutes, more preferably at least 30 minutes, further preferably at least 60 minutes.
- aging means that the crystallized trimanganese tetraoxide particles are made to stay in the slurry.
- the oxidizing agent is not particularly limited and may, for example, be an oxygen-containing gas (including the air) or hydrogen peroxide. It is preferred to use as the oxidizing agent an oxygen-containing gas, more preferably the air, which can be used easily.
- the obtained trimanganese tetraoxide particles are secondary particles having primary particles agglomerated with an appropriate strength, and are easily ground. Accordingly, so long as the above oxidation-reduction potential and manganese molar ratio and solid content concentration of the obtained slurry are satisfied, the method of mixing the manganese salt aqueous solution with the alkali aqueous solution is optional.
- the mixing method may, for example, be a method of directly mixing the manganese salt aqueous solution with the alkali aqueous solution so that the oxidation-reduction potential and the manganese molar ratio are within the ranges of the present invention, or a method of adding the manganese salt aqueous solution and the alkali aqueous solution to a solvent such as water or a slurry so that the oxidation-reduction potential and the manganese molar ratio are within the ranges of the present invention, followed by mixing.
- the mixing method is preferably a method of adding the manganese salt aqueous solution and the alkali aqueous solution to a solvent, followed by mixing.
- the manganese salt aqueous solution and the alkali aqueous solution are mixed so that the oxidation-reduction potential and the manganese molar ratio in the solvent are within the ranges of the present invention.
- a more preferred mixing method may, for example, be a method of adding the manganese salt aqueous solution and the alkali aqueous solution to the solvent respectively at constant rates to the solvent, followed by mixing, or a method of adding the manganese salt aqueous solution and the alkali aqueous solution to the solvent at addition rates such that the manganese molar ratio of the manganese salt aqueous solution and the alkali aqueous solution is within a range of the manganese molar ratio of the present invention, followed by mixing.
- a more preferred mixing method may, for example, be a method in which a solvent which contains no manganese ions such as water is used, and the manganese salt aqueous solution and the alkali aqueous solution are added to the solvent at addition rates such that the manganese molar ratio of the manganese salt aqueous solution and the alkali aqueous solution is within a range of the manganese molar ratio of the present invention, followed by mixing.
- a solvent which contains no manganese ions such as water
- the manganese salt aqueous solution and the alkali aqueous solution are added to the solvent at addition rates such that the manganese molar ratio of the manganese salt aqueous solution and the alkali aqueous solution is within a range of the manganese molar ratio of the present invention, followed by mixing.
- the complexing agent in the present invention means ammonia, an ammonium salt, hydrazine or EDTA, or one having the same complexing ability as those.
- trimanganese tetraoxide particles obtained in the presence of a complexing agent tend to be one differing in the pore volume, the agglomeration state, etc. from the trimanganese tetraoxide particles of the present invention.
- trimanganese tetraoxide particles which are readily ground can be produced, but also trimanganese tetraoxide particles comprising primary particles agglomerated, having high reactivity with a lithium compound, can be produced.
- trimanganese tetraoxide particles obtained by the production process of the present invention may be fired to be converted to manganese sesquioxide.
- the trimanganese tetraoxide particles of the present invention may be used as a manganese material of a lithium manganese oxide. Now, a process for producing a lithium oxide using the trimanganese tetraoxide particles of the present invention as a manganese material will be described.
- the process for producing a lithium oxide of the present invention comprises a mixing step of mixing the above trimanganese tetraoxide particles with at least one of lithium and a lithium compound, and a heating step of subjecting the mixture to heat treatment.
- another metal compound may be added so as to improve the characteristics of a lithium secondary battery cathode material of the lithium oxide.
- another metal compound has a metal element different from manganese and lithium as a constituting element.
- it is a compound containing as a constituting element at least one member selected from the group consisting of Al, Mg, Ni, Co, Cr, Ti and Zr. The same effects will be obtained even when such another metal compound is added.
- the lithium compound may be any compound.
- the lithium compound may, for example, be lithium hydroxide, lithium oxide, lithium carbonate, lithium iodide, lithium nitrate, lithium oxalate or an alkyllithium.
- a preferred lithium compound may, for example, be lithium hydroxide, lithium oxide or lithium carbonate.
- the lithium oxide obtained by using the trimanganese tetraoxide of the present invention as a material may be used as a cathode active material of a lithium ion secondary battery.
- a sample was observed by a commercially available scanning electron microscope (tradename: JSM-6390LV model, manufactured by JEOL Ltd.). SEM observation was carried out with respect to the surface and the cross section of the sample. Further, SEM observation of the cross section was carried out with respect to a plane obtained in such a manner that the sample was embedded in a resin and cut, and the cut surface was polished to obtain a smooth plane.
- JSM-6390LV model manufactured by JEOL Ltd.
- a commercially available particle size measuring apparatus (tradename: MICROTRAC HRA 9320-X100, manufactured by Nikkiso Co., Ltd.) was used. Further, before measurement, the sample was dispersed in pure water to obtain a measurement solution, and ammonia water was added thereto to adjust the pH to be 8.5.
- the crystal phase of a sample was measured by X-ray diffraction.
- the BET specific surface area of a sample was measured by nitrogen adsorption by a BET one point method.
- the sample used for measurement of the BET specific surface area was heated at 150° C. for 40 minutes for deaeration prior to measurement of the BET specific surface area.
- a sample was dissolved in a mixed aqueous solution of hydrochloric acid and hydrogen peroxide, and the Na, Mg, Ca, Li, SO 4 2 ⁇ and Mn contents were obtained by an ICP method.
- the pore distribution of a sample was determined by a mercury intrusion technique. Pore distribution measurement was carried out using a commercially available mercury porosimeter (tradename: Pore sizer 9510 manufactured by Micromeritics), under a pressure within a range of from the atmospheric pressure to 414 MPa. The diameter of pores which can be measured within such a pressure range is within a range of at least 0.003 ⁇ m and at most 400 ⁇ m.
- the ratio of the volume of pores having a diameter of at most 10 ⁇ m to the accumulation of the pore volume obtained by the pore distribution measurement was determined and taken as the pore volume ratio of pores having a diameter of at most 10 ⁇ m.
- the pore volume ratio of pores having a diameter of at most 2 ⁇ m was similarly obtained.
- the pores with the most frequent diameter in the pore volume obtained by the pore distribution measurement were regarded as the most frequent pores.
- the ratio of the area of pores having a diameter of at most 0.1 ⁇ m to the accumulation of the pore area obtained by the pore distribution measurement was obtained and taken as the pore area ratio of pores of at most 10 ⁇ m.
- the pore area ratio of pores having a diameter of at most 0.05 ⁇ m was similarly obtained. Further, as a pretreatment for the pore distribution measurement, the sample was dried by being left at rest at 100° C.
- the manganese sulfate aqueous solution and the sodium hydroxide aqueous solution were continuously added to the mixed reaction slurry so that OH ⁇ /Mn 2+ (mol/mol) of the sodium hydroxide aqueous solution and the manganese sulfate aqueous solution added (hereinafter referred to as “manganese molar ratio”) would be 0.46.
- the rate of withdrawal of the mixed reaction slurry was adjusted, and reaction was carried out for 8 hours while the solid content concentration of trimanganese tetraoxide in the mixed reaction slurry was adjusted to be 0.95 wt %.
- the mixed reaction slurry was recovered, subjected to filtration, washed and dried to obtain manganese oxide.
- the density by the measurement method in accordance with JIS R1628 (hereinafter referred to as “JIS density”) was measured.
- JIS density the density by the measurement method in accordance with JIS R1628
- the JIS density of the trimanganese tetraoxide in Example 1 was 1.54 g/cm 3 , which was 1.1 times the tap density.
- Manganese oxide was obtained in the same manner as in Example 1 except that the reaction time was 1.5 hours.
- Manganese oxide was obtained in the same manner as in Example 1 except that the concentration of the manganese sulfate aqueous solution was 0.2 mol/L, and the reaction time was 9 hours.
- Manganese oxide was obtained in the same manner as in Example 1 except that the concentration of the manganese sulfate aqueous solution was 0.2 mol/L, the solid content concentration of trimanganese tetraoxide in the mixed reaction slurry was 0.56 wt %, and the reaction time was 30 minutes.
- Manganese oxide was obtained in the same manner as in Example 1 except that after manganese oxide was precipitated, the rate of withdrawal of the mixed reaction slurry was adjusted and the reaction was carried out for 48 hours while the solid content concentration of trimanganese tetraoxide in the mixed reaction slurry was adjusted to be 5.46 wt %.
- the trimanganese tetraoxide in Comparative Example 1 had a high fillability with a tap density of 2.2 g/cm 3 , but the average primary particle size was large, and the pore volume was small.
- Trimanganese tetraoxide of the present invention is excellent in the handleability and is suitably used as a manganese material of a lithium manganese oxide which is industrially easily handled.
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Abstract
Trimanganese tetraoxide has high reactivity with a lithium compound, is excellent in handling efficiency, and is suitable as a manganese material of a lithium manganese oxide, and its production process. Trimanganese tetraoxide particles including trimanganese tetraoxide primary particles having an average primary particle size of at most 2 μm agglomerated, the pore volume of pores being at least 0.4 mL/g. The most frequent pores are preferably pores having a diameter of at most 5 μm. The trimanganese tetraoxide particles can be obtained by producing trimanganese tetraoxide particles, which includes directly crystallizing trimanganese tetraoxide from a manganese salt aqueous solution, wherein the manganese salt aqueous solution and an alkali aqueous solution are mixed so that the oxidation-reduction potential is at least 0 mV and OH−/Mn2+ (mol/mol) is at most 0.55, to obtain a slurry, and the solid content concentration of the slurry is adjusted to be at most 2 wt %.
Description
The present invention relates to trimanganese tetraoxide suitable as a manganese material of a cathode active material of a lithium ion secondary battery, and its production process.
A lithium manganese oxide is used as a cathode active material for a lithium ion secondary battery. As its manganese material, electrolytic manganese dioxide is widely used. Further, trimanganese tetraoxide is also used as a preferred manganese material of a lithium manganese oxide, whereby the fillability of the obtained lithium manganese oxide tends to improve (for example, Patent Documents 1 and 2).
Trimanganese tetraoxide is converted to a lithium manganese oxide by being mixed with a lithium material and another metal material, followed by firing. For example, rhombic LiMnO2 obtained by mixing and grinding lithium hydroxide and trimanganese tetraoxide, followed by firing, has been reported (Patent Document 1). Further, a lithium nickel manganese cobalt oxide obtained by forming lithium carbonate, trimanganese tetraoxide, cobalt oxyhydroxide, nickel hydroxide and the like into a slurry, and wet grinding the slurry, followed by firing, has been reported (Patent Document 2).
As mentioned above, trimanganese tetraoxide to be a manganese material of a lithium manganese oxide, which is used as mixed with another material, is required to have high mixing properties with another material, that is, to be uniformly mixed with another material.
As trimanganese tetraoxide to be a manganese material of a lithium manganese oxide, for the purpose of uniform mixing, trimanganese tetraoxide having a maximum particle size of at most 150 nm, obtained by mixing a manganese-containing liquid with an alkali liquid, followed by oxidation, has been reported (Patent Document 3). Further, trimanganese tetraoxide having a large average primary particle size of from 3.0 to 15 μm and having a low Na content and a low S content, in order to obtain lithium manganate particle powder having a large primary particle size and having a small amount of agglomerated particles, has been reported (Patent Document 4).
Patent Document 1: JP-A-2003-086180
Patent Document 2: JP-A-2012-023015
Patent Document 3: JP-A-2001-261343
Patent Document 4: JP-A-2004-292264
The trimanganese tetraoxide in Patent Document 3 has a very small average particle size of at most 100 nm and has a high dispersibility. Accordingly, it has a relatively high reactivity with a lithium compound, but has a poor flowability and is hardly industrially handled.
The trimanganese tetraoxide in Patent Document 4 has a large primary particle size and thus is excellent in the dispersibility. However, since it comprises large primary particles, it has a low reactivity with a lithium compound, and the battery performances particularly the output characteristics of a lithium manganese oxide obtained from it as a material are not sufficient.
The object of the present invention is to solve such problems and to provide trimanganese tetraoxide suitable as a manganese material of a lithium manganese oxide and its production process.
The present inventors have conducted extensive studies on trimanganese tetraoxide used as a material of a lithium manganese oxide and its production process. As a result, they have found that trimanganese tetraoxide particles comprising secondary particles having primary particles agglomerated with an appropriate strength can be a manganese material of a lithium manganese oxide with excellent handleability, without a decrease of a reactivity with a lithium compound.
That is, the present invention provides the following.
- (1) Trimanganese tetraoxide particles comprising trimanganese tetraoxide primary particles having an average primary particle size of at most 2 μm agglomerated, the pore volume of pores being at least 0.4 mL/g.
- (2) The trimanganese tetraoxide particles according to the above (1), wherein the most frequent pores are pores having a diameter of at most 5 μm.
- (3) The trimanganese tetraoxide particles according to the above (1) or (2), wherein the pore volume ratio of pores having a diameter of at least 10 μm as measured by a mercury intrusion technique is at most 20%.
- (4) The trimanganese tetraoxide particles according to any one of the above (1) to (3), wherein the average particle size is at least 5 μm and at most 50 μm.
- (5) The trimanganese tetraoxide particles according to any one of the above (1) to (4), wherein the modal particle size is larger than the average particle size.
- (6) The trimanganese tetraoxide particles according to any one of the above (1) to (5), wherein the content of sulfate ions is at most 0.5 wt %.
- (7) The trimanganese tetraoxide particles according to any one of the above (1) to (6), wherein the average primary particle size is larger than 0.2 μm and at most 0.5 μm.
- (8) The trimanganese tetraoxide particles according to any one of the above (1) to (7), wherein the pore volume of pores is at most 2 mL/g.
- (9) A process for producing the trimanganese tetraoxide particles as defined in any one of the above (1) to (8), which comprises a crystallization step of directly crystallizing trimanganese tetraoxide from a manganese salt aqueous solution, wherein in the crystallization step, the manganese salt aqueous solution and an alkali aqueous solution are mixed so that the oxidation-reduction potential is at least 0 mV and OH−/Mn2+ (mol/mol) is at most 0.55, to obtain a slurry, and the solid content concentration of the slurry is adjusted to be at most 2 wt %.
- (10) The production process according to the above (9), wherein the oxidation-reduction potential is at least 60 mV and at most 200 mV.
- (11) The production process according to the above (9) or (10), wherein in the crystallization step, the slurry having a solid content concentration of at most 2 wt % is aged for at least 10 minutes.
- (12) The production process according to any one of the above (9) to (11), wherein the temperature of the manganese salt aqueous solution is at least 60° C. and at most 95° C.
- (13) The production process according to any one of the above (9) to (12), wherein OH−/Mn2+ (mol/mol) is at least 0.35.
- (14) A process for producing a lithium oxide, which comprises a mixing step of mixing the trimanganese tetraoxide particles as defined in any one of the above (1) to (8) with a lithium compound, and a heating step of subjecting the mixture to heat treatment.
According to the present invention, it is possible to provide porous trimanganese tetraoxide particles which have an appropriate strength since primary particles are present even in their interior, and which are easily ground. Thus, the trimanganese tetraoxide particles are easily handled e.g. in a transport step, and by grinding the particles at the time of mixing, the primary particles are dispersed, and the reactivity with a lithium compound or the like will not be lowered. Accordingly, the trimanganese tetraoxide particles are excellent in the handleability and can be a manganese material of a lithium manganese oxide which is easily handled industrially. Further, since the trimanganese tetraoxide particles of the present invention homogeneously have pores even in the interior of the particles, removal of the impurities is easy.
Further, according to the process for producing the trimanganese tetraoxide, such trimanganese tetraoxide particles can easily and continuously be produced.
Now, the trimanganese tetraoxide particles of the present invention will be described.
The trimanganese tetraoxide particles of the present invention comprise particles having trimanganese tetraoxide having an average primary particle size of at most 2 μm agglomerated, that is, secondary particles having trimanganese tetraoxide primary particles having an average particle size of at most 2 μm agglomerated. The average primary particle size is preferably at most 1 μm, more preferably at most 0.5 μm, further preferably at most 0.45 μm, still further preferably at most 0.4 μm. By the average primary particle size being at most 2 μm, the reactivity with a lithium compound tends to be high.
The average primary particle size i.e. the average particle size of the trimanganese tetraoxide primary particles is preferably at least 0.1 μm, more preferably larger than 0.2 μm.
The trimanganese tetraoxide particles of the present invention are particles having trimanganese tetraoxide having an average primary particle size of at most 2 μm agglomerated. By agglomeration of primary particles, the flowability of a powder tends to be high, whereby the handleability before the mixing step tends to improve. Further, by grinding the trimanganese tetraoxide particles of the present invention when mixed with a lithium compound and the like, the primary particles constituting the trimanganese tetraoxide particles of the present invention are dispersed, and mixing with a lithium compound and the like is possible while maintaining the high reactivity with them.
In the present invention, “primary particles” are particles of minimum unit which can be confirmed as separate particles by scanning electron microscope observation.
The trimanganese tetraoxide particles of the present invention form pores by agglomeration of the primary particles. The pore volume of the pores is at least 0.4 mL/g, preferably at least 0.5 mL/g, more preferably at least 0.7 mL/g, whereby the trimanganese tetraoxide particles of the present invention are easily ground. If the pore volume of the pores is less than 0.4 mL/g, agglomeration of the primary particles tends to be too strong, and the trimanganese tetraoxide particles are hardly ground. The pore volume of the pores of the trimanganese tetraoxide particles of the present invention tends to be at most 2 mL/g, further at most 1.5 mL/g, still further at most 1 mL/g.
The trimanganese tetraoxide particles of the present invention are particles excellent in the handleability and the grinding property only if both of the average primary particle size and the pore volume are satisfied.
The shape of the trimanganese tetraoxide particles of the present invention is a sphere, preferably a sphere having pores on its surface. By the shape of the trimanganese tetraoxide particles of the present invention being a sphere, their fillability tends to be high. In the present invention, a sphere means a sphere having an acute angle portion or a sphere not in the form of a polyhedron, and it includes not only a true sphere but also a distorted sphere such as an approximate sphere, or such a sphere having pores on its surface.
In the trimanganese tetraoxide particles of the present invention, the most frequent pores are preferably pores having a diameter of at most 5 μm, more preferably pores having a diameter of at most 4 μm, further preferably pores having a diameter of at most 3 μm. The most frequent pores are pores with a largest volume among pores which the trimanganese tetraoxide particles of the present invention have. When the most frequent pores are pores having a diameter of at most 5 μm, the trimanganese tetraoxide particles of the present invention have a pore structure such that the primary particles are present even in their interior and the pores are uniformly dispersed in the particles, not a pore structure of a so-called hollow sphere such as a table tennis ball. Thus, the trimanganese tetraoxide particles of the present invention have an appropriate strength even though they are easily ground.
With a view to maintaining the easy grinding property, the most frequent pores are preferably pores having a diameter of at least 1 μm, more preferably pores having a diameter of at least 2 μm.
The trimanganese tetraoxide particles of the present invention have a pore volume ratio of pores having a diameter of at least 10 μm as measured by a mercury intrusion technique (hereinafter referred to simply as “a pore volume ratio of pores having a diameter of at least 10 μm”) of preferably at most 20%, more preferably at most 15%, further preferably at most 10%. By the pore volume ratio of pores having a diameter of at least 10 μm being at most 20%, the reactivity with a lithium compound tends to be uniform.
In the present invention, “the pore volume ratio” is a ratio of the total volume of pores having a diameter within a predetermined range (for example, pores having a pore diameter of at least 10 μm) to the total volume of all the pores of the trimanganese tetraoxide particles. The diameter distribution and the pore volume of pores can be measured by a commercially available porosimeter employing a mercury intrusion technique.
The trimanganese tetraoxide particles of the present invention have a pore area ratio of pores having a diameter of at most 0.1 μm as measured by a mercury intrusion technique (hereinafter referred to simply as “a pore area ratio of pores having a diameter of at most 0.1 μm”) of preferably at least 1.5%, more preferably at least 5%. By the amount of fine pores having a diameter of at most 0.1 μm being within the above range, the trimanganese tetraoxide particles are readily washed, whereby impurities are likely to be removed.
“The pore area ratio” in the present invention is a ratio of the total area of pores having a diameter within a predetermined range (for examples, pores having a pore diameter of at most 0.1 μm) to the total area of all the pores of the trimanganese tetraoxide. The diameter distribution and the pore area of pores may be measured by a commercially available porosimeter employing a mercury intrusion technique.
The BET specific surface area of the trimanganese tetraoxide particles of the present invention is optional so long as the particles have the above pore volume. For example, the BET specific surface area of the trimanganese tetraoxide particles of the present invention may be at least 2 m2/g, further at least 3 m2/g, still further at least 5m2/g.
The trimanganese tetraoxide particles of the present invention are ground when mixed with a lithium compound. Accordingly, the fillability as the trimanganese tetraoxide particles is not particularly limited, however, the tap density may, for example, be less than 1.5 g/cm3, further at most 1.4 g/cm3.
Of the trimanganese tetraoxide particles of the present invention, the particle size distribution may not be monomodal, and the modal particle size and the average particle size may be different from each other.
The modal particle size is a particle size with the highest frequency.
Of the trimanganese tetraoxide particles of the present invention, the modal particle size tends to be larger than the average particle size (that is, the modal particle size>the average particle size). Accordingly, the modal particle size may be at least 1.05 times the average particle size (that is, the modal particle size/the average particle size≧1.05), further at least 1.1 times (that is, the modal particle size/the average particle size≧1.1), further at least 1.3 times (that is, the modal particle size/the average particle size≧1.3).
The specific modal particle size may be at least 6 μm, further at least 9 μm, particularly at least 11 μm.
“The tap density” in the present invention is an apparent density of a powder obtained by tapping a container under specific conditions. Accordingly, it is different from a so-called press density i.e. a density of a powder in a state where the powder is packed in a container and pressure-molded under a certain pressure. The tap density may be measured, for example, by a method disclosed in the after-mentioned Examples.
The particle size of the trimanganese tetraoxide particles of the present invention is optional so long as the particles have the above pore volume. For example, the average particle size of the trimanganese tetraoxide particles of the present invention may be at least 5 μm, preferably at least 10 μm. On the other hand, the upper limit of the average particle size may be at most 50 μm, further at most 20 μm.
The average particle size of the trimanganese tetraoxide particles of the present invention means an average particle size of secondary particles having trimanganese tetraoxide having an average primary particle size of at most 2 μm agglomerated.
In the present invention, the average particle sizes of the primary particles and the secondary particles are both volume average particle sizes.
The crystal structure of trimanganese tetraoxide constituting the trimanganese tetraoxide particles is a spinel structure. This crystal structure shows the same X-ray diffraction pattern as No. 24-734 X-ray diffraction pattern of the JCPDS pattern.
The chemical formula of trimanganese tetraoxide is represented as Mn3O4. Accordingly, in a case where trimanganese tetraoxide is represented by MnOx, the ratio x of the oxygen element to the manganese element is from 1.33 to 1.34. However, the ratio x of oxygen to manganese of trimanganese tetraoxide constituting the trimanganese tetraoxide particles of the present invention is not limited to 1.33 to 1.34. The trimanganese tetraoxide of the present invention has the above crystal structure, and may be a manganese oxide represented by MnOx wherein x is within a range of from 1.20 to 1.40. x is preferably from 1.25 to 1.40, more preferably from 1.30 to 1.40.
In order to obtain long charge and discharge cycle life, the trimanganese tetraoxide particles of the present invention have a Ca content of preferably at most 100 wtppm, more preferably at most 60 wtppm, particularly preferably at most 30 wtppm. The Ca content is preferably lower. However, even if the trimanganese tetraoxide particles contain 5 wtppm of Ca, there is substantially no influence when used as a material for a lithium manganese oxide.
In order to obtain long charge and discharge cycle life, the trimanganese tetraoxide particles of the present invention have a Mg content of preferably at most 50 wtppm, particularly preferably at most 20 wtppm. Further, the Mg content is preferably lower. However, even if the trimanganese tetraoxide particles contain 1 wtppm of Mg, there is substantially no influence when used as a material for a lithium manganese oxide.
In order to obtain long charge and discharge cycle life, the trimanganese tetraoxide particles of the present invention preferably have a low content of sulfate ions (SO4 2−) as impurities. The content of sulfate ions in the manganese oxide is preferably at most 1 wt %, more preferably at most 0.5 wt %, further preferably at most 0.3 wt %.
Now, the process for producing the trimanganese tetraoxide particles of the present invention will be described.
The trimanganese tetraoxide particles of the present invention may be produced by a process for producing trimanganese tetraoxide particles, which comprises a crystallization step of directly crystallizing trimanganese tetraoxide from a manganese salt aqueous solution, wherein in the crystallization step, the manganese salt aqueous solution and an alkali aqueous solution are mixed so that the oxidation-reduction potential is at least 0 mV and OH−/Mn2+ (mol/mol) (hereinafter referred to as “manganese molar ratio”) is at most 0.55 to obtain a slurry, and the solid content concentration of the slurry is adjusted to be at most 2 wt %.
The present invention provides a process for producing trimanganese tetraoxide particles comprising a crystallization step of directly crystallizing trimanganese tetraoxide from a manganese salt aqueous solution. “Directly crystallizing trimanganese tetraoxide” means that trimanganese tetraoxide is obtained not by means of manganese hydroxide from a manganese salt aqueous solution. Such includes an embodiment such that a crystal phase of manganese hydroxide does not form at all from the manganese salt aqueous solution and an embodiment such that fine crystals of manganese hydroxide are precipitated in a short time and then they are converted to trimanganese tetraoxide before they grow into hexagonal plate-form crystals.
Accordingly, the crystallization step of the present invention does not have a step of precipitating manganese hydroxide crystals from a manganese salt aqueous solution and oxidizing them by an oxidizing agent.
The production process of the present invention comprises in the crystallization step a step of mixing the manganese salt aqueous solution with an alkali aqueous solution so that the above oxidation-reduction potential and manganese molar ratio are satisfied, whereby trimanganese tetraoxide can be directly crystallized from the manganese salt aqueous solution. That is, in the production process of the present invention, trimanganese tetraoxide can be precipitated without a step of forming crystals of manganese hydroxide from the manganese aqueous solution.
Here, “trimanganese tetraoxide is directly precipitated from the manganese aqueous solution” means that hexagonal plate-form crystals of manganese hydroxide do not form from the manganese aqueous solution, and such includes an embodiment such that a crystal phase of manganese hydroxide do not form at all and an embodiment such that fine crystals of manganese hydroxide are precipitated in a short time and they are converted to trimanganese tetraoxide before they grow into hexagonal plate-form crystals.
Further, whether the hexagonal plate-form crystals of manganese hydroxide are formed or not can be judged by observing the particle shape of the obtained trimanganese tetraoxide.
A conventional production process comprises a step of forming manganese hydroxide from a manganese aqueous solution in a reducing atmosphere first and then a step of oxidizing it in an oxidizing atmosphere such as in oxygen or in the air to form trimanganese tetraoxide. In such a production process, it is necessary to change the reaction atmosphere in the middle of the step to obtain trimanganese tetraoxide. Thus, by such a production process by means of manganese hydroxide, trimanganese tetraoxide cannot be continuously produced, or the production process tends to be complicated.
Whereas, by the production process of the present invention, trimanganese tetraoxide is directly crystallized from the manganese salt aqueous solution by producing trimanganese tetraoxide with the above oxidation-reduction potential and manganese molar ratio. Accordingly, in the production process of the present invention, it is not necessary to change the atmosphere in the middle of the step. As mentioned above, in the production process of the present invention, it is not necessary to change the atmosphere during production, and thus trimanganese tetraoxide particles can be continuously produced by mixing a manganese salt aqueous solution with an alkali aqueous solution.
The manganese salt aqueous solution used in the production process of the present invention may be an aqueous solution containing manganese ions, and may, for example, be an aqueous solution of manganese sulfate, manganese chloride, manganese nitrate, manganese acetate or the like, or a solution having metal manganese, manganese oxide or the like dissolved in an acid aqueous solution of e.g. sulfuric acid, hydrochloric acid, nitric acid or acetic acid.
The manganese ion concentration of the manganese salt aqueous solution may be an optional concentration, and for example, the manganese ion concentration is preferably at least 0.1 mol/L. By the manganese ion concentration of the manganese salt aqueous solution being at least 0.1 mol/L, the trimanganese tetraoxide particles will efficiently be obtained.
The temperature of the manganese salt aqueous solution is preferably at least 40° C., more preferably at least 60° C. and at most 95° C., further preferably at least 70° C. and at most 80° C. By the temperature of the manganese salt aqueous solution at the time of precipitation being within such a range, crystallization of the trimanganese tetraoxide tends to be accelerated, and the particle size of the trimanganese tetraoxide tends to be uniform.
The alkali aqueous solution used in the production process of the present invention may be an aqueous solution showing alkalinity, and may, for example, be an aqueous solution of e.g. sodium hydroxide or potassium hydroxide.
The concentration of the alkali aqueous solution is not limited, and is optional in relation to the concentration of the manganese salt aqueous solution to achieve the manganese molar ratio of the present invention. For example, the concentration of hydroxide ions (OH−) of the alkali aqueous solution may, for example, be at least 0.1 mol/L, further at least 0.2 mol/L.
The step of mixing the manganese salt aqueous solution with the alkali aqueous solution is carried out at an oxidation-reduction potential of at least 0 mV. If the oxidation-reduction potential is less than 0 mV, a manganese oxide other than the trimanganese tetraoxide will form. In order that the trimanganese tetraoxide is readily crystallized directly from manganese ions, the oxidation-reduction potential is preferably at least 40 mV, more preferably at least 60 mV, further preferably at least 80 mV.
By the oxidation-reduction potential being high, a trimanganese tetraoxide single phase is readily obtained, and when it is at most 300 mV, further at most 200 mV, single phase trimanganese tetraoxide is more readily obtained. The oxidation-reduction potential may be obtained as a value to the standard hydrogen electrode (SHE).
The manganese salt aqueous solution is mixed with the alkali aqueous solution so that the manganese molar ratio is at most 0.55. If the manganese molar ratio exceeds 0.55, a single phase of trimanganese tetraoxide is hardly obtained. The manganese molar ratio is preferably at most 0.52, more preferably at most 0.5.
Further, the manganese molar ratio is at least 0.35, preferably at least 0.4, more preferably at least 0.45, whereby the trimanganese tetraoxide particles will efficiently be produced.
By mixing the manganese salt aqueous solution with the alkali aqueous solution, trimanganese tetraoxide is crystallized and a slurry containing the trimanganese tetraoxide is obtained. The solid content concentration of the slurry is at most 2 wt %, preferably at most 1.5 wt %, more preferably at most 1 wt %. By adjusting the solid content concentration of the slurry to be at most 2 wt %, secondary particles having primary particles of trimanganese tetraoxide agglomerated with an appropriate strength will form, whereby the trimanganese tetraoxide particles of the present invention are easily ground. From the viewpoint of the production efficiency, the lower limit of the solid content concentration of the slurry may, for example, be at least 0.1 wt % as the solid content concentration. Here, the solid content concentration means the concentration of trimanganese tetraoxide in the slurry.
The solid content concentration of the slurry is preferably within the above range and constant. By the solid content concentration of the slurry being constant, the obtained trimanganese tetraoxide particles are likely to be homogeneously ground. As a method of adjusting the solid content concentration of the slurry to be constant, a method of withdrawing a part of the slurry simultaneously with mixing of the manganese salt aqueous solution with the alkali aqueous solution may, for example, be mentioned.
In the crystallization step, it is preferred that trimanganese tetraoxide is aged in the slurry, whereby agglomeration of the primary particles is accelerated, and trimanganese tetraoxide particles having an appropriate size are likely to be obtained. From the industrial viewpoint, the ageing time is preferably at least 10 minutes, more preferably at least 30 minutes, further preferably at least 60 minutes.
Here, aging means that the crystallized trimanganese tetraoxide particles are made to stay in the slurry.
In the process for producing the trimanganese tetraoxide particles of the present invention, it is preferred to crystallize the trimanganese tetraoxide using an oxidizing agent. The oxidizing agent is not particularly limited and may, for example, be an oxygen-containing gas (including the air) or hydrogen peroxide. It is preferred to use as the oxidizing agent an oxygen-containing gas, more preferably the air, which can be used easily.
In the production process of the present invention, when the manganese salt aqueous solution and the alkali aqueous solution are mixed with the above oxidation-reduction potential and manganese molar ratio satisfied, and the solid content concentration of the slurry thus obtained is satisfied, the obtained trimanganese tetraoxide particles are secondary particles having primary particles agglomerated with an appropriate strength, and are easily ground. Accordingly, so long as the above oxidation-reduction potential and manganese molar ratio and solid content concentration of the obtained slurry are satisfied, the method of mixing the manganese salt aqueous solution with the alkali aqueous solution is optional.
The mixing method may, for example, be a method of directly mixing the manganese salt aqueous solution with the alkali aqueous solution so that the oxidation-reduction potential and the manganese molar ratio are within the ranges of the present invention, or a method of adding the manganese salt aqueous solution and the alkali aqueous solution to a solvent such as water or a slurry so that the oxidation-reduction potential and the manganese molar ratio are within the ranges of the present invention, followed by mixing.
With a view to sufficiently and uniformly reacting the manganese salt aqueous solution with the alkali aqueous solution, the mixing method is preferably a method of adding the manganese salt aqueous solution and the alkali aqueous solution to a solvent, followed by mixing. In such a case, the manganese salt aqueous solution and the alkali aqueous solution are mixed so that the oxidation-reduction potential and the manganese molar ratio in the solvent are within the ranges of the present invention. A more preferred mixing method may, for example, be a method of adding the manganese salt aqueous solution and the alkali aqueous solution to the solvent respectively at constant rates to the solvent, followed by mixing, or a method of adding the manganese salt aqueous solution and the alkali aqueous solution to the solvent at addition rates such that the manganese molar ratio of the manganese salt aqueous solution and the alkali aqueous solution is within a range of the manganese molar ratio of the present invention, followed by mixing. A more preferred mixing method may, for example, be a method in which a solvent which contains no manganese ions such as water is used, and the manganese salt aqueous solution and the alkali aqueous solution are added to the solvent at addition rates such that the manganese molar ratio of the manganese salt aqueous solution and the alkali aqueous solution is within a range of the manganese molar ratio of the present invention, followed by mixing. By adding and mixing the manganese salt aqueous solution and the alkali aqueous solution in such a manner, not only the solid content concentration of the obtained slurry is readily controlled, but also continuous production of the trimanganese tetraoxide particles is more readily carried out.
In the process for producing the trimanganese tetraoxide particles of the present invention, it is preferred not to use a complexing agent when the manganese salt aqueous solution and the alkali aqueous solution are mixed. The complexing agent in the present invention means ammonia, an ammonium salt, hydrazine or EDTA, or one having the same complexing ability as those.
Such a complexing agent influences the trimanganese tetraoxide precipitation behavior. Accordingly, the trimanganese tetraoxide particles obtained in the presence of a complexing agent tend to be one differing in the pore volume, the agglomeration state, etc. from the trimanganese tetraoxide particles of the present invention.
As mentioned above, according to the production process of the present invention, not only trimanganese tetraoxide particles which are readily ground can be produced, but also trimanganese tetraoxide particles comprising primary particles agglomerated, having high reactivity with a lithium compound, can be produced.
The trimanganese tetraoxide particles obtained by the production process of the present invention may be fired to be converted to manganese sesquioxide.
The trimanganese tetraoxide particles of the present invention may be used as a manganese material of a lithium manganese oxide. Now, a process for producing a lithium oxide using the trimanganese tetraoxide particles of the present invention as a manganese material will be described.
The process for producing a lithium oxide of the present invention comprises a mixing step of mixing the above trimanganese tetraoxide particles with at least one of lithium and a lithium compound, and a heating step of subjecting the mixture to heat treatment.
In the mixing step, when the trimanganese tetraoxide particles are mixed with a lithium compound, another metal compound may be added so as to improve the characteristics of a lithium secondary battery cathode material of the lithium oxide. Such another metal compound has a metal element different from manganese and lithium as a constituting element. For example, it is a compound containing as a constituting element at least one member selected from the group consisting of Al, Mg, Ni, Co, Cr, Ti and Zr. The same effects will be obtained even when such another metal compound is added.
The lithium compound may be any compound. The lithium compound may, for example, be lithium hydroxide, lithium oxide, lithium carbonate, lithium iodide, lithium nitrate, lithium oxalate or an alkyllithium. A preferred lithium compound may, for example, be lithium hydroxide, lithium oxide or lithium carbonate.
The lithium oxide obtained by using the trimanganese tetraoxide of the present invention as a material may be used as a cathode active material of a lithium ion secondary battery.
Now, the present invention will be described with reference to Examples. However, the present invention is by no means restricted to such specific Examples. Evaluations in Examples and Comparative Examples were carried out as follows.
(Tap Density)
The density after 5 g of a sample was filled in a 10 mL measuring cylinder and tapped 200 times was taken as the tap density.
(SEM Observation)
A sample was observed by a commercially available scanning electron microscope (tradename: JSM-6390LV model, manufactured by JEOL Ltd.). SEM observation was carried out with respect to the surface and the cross section of the sample. Further, SEM observation of the cross section was carried out with respect to a plane obtained in such a manner that the sample was embedded in a resin and cut, and the cut surface was polished to obtain a smooth plane.
(Average Primary Particle Size)
In a SEM photograph of the surface of a sample with a magnification of 10,000 times, the particle sizes of 100 or more particles were measured and averaged to obtain the average primary particle size.
(Average Particle Size and Standard Deviation of Particle Size)
To measure the average particle size and the modal particle size of trimanganese tetraoxide particles, a commercially available particle size measuring apparatus (tradename: MICROTRAC HRA 9320-X100, manufactured by Nikkiso Co., Ltd.) was used. Further, before measurement, the sample was dispersed in pure water to obtain a measurement solution, and ammonia water was added thereto to adjust the pH to be 8.5.
(X-Ray Diffraction Measurement)
The crystal phase of a sample was measured by X-ray diffraction. For measurement, a conventional X-ray diffraction apparatus was used. Measurement was carried out using CuKα radiation (λ=1.5405 Å) as the light source with a step scanning as the measurement mode under scanning conditions of 0.04° per second for a measuring time of 3 seconds within a measurement range 2θ of from 5° to 80°.
(BET Specific Surface Area)
The BET specific surface area of a sample was measured by nitrogen adsorption by a BET one point method. The sample used for measurement of the BET specific surface area was heated at 150° C. for 40 minutes for deaeration prior to measurement of the BET specific surface area.
(Chemical Composition Analysis)
A sample was dissolved in a mixed aqueous solution of hydrochloric acid and hydrogen peroxide, and the Na, Mg, Ca, Li, SO4 2− and Mn contents were obtained by an ICP method.
(Pore Distribution Measurement)
In the present invention, the pore distribution of a sample was determined by a mercury intrusion technique. Pore distribution measurement was carried out using a commercially available mercury porosimeter (tradename: Pore sizer 9510 manufactured by Micromeritics), under a pressure within a range of from the atmospheric pressure to 414 MPa. The diameter of pores which can be measured within such a pressure range is within a range of at least 0.003 μm and at most 400 μm.
The ratio of the volume of pores having a diameter of at most 10 μm to the accumulation of the pore volume obtained by the pore distribution measurement was determined and taken as the pore volume ratio of pores having a diameter of at most 10 μm. The pore volume ratio of pores having a diameter of at most 2 μm was similarly obtained.
Further, the pores with the most frequent diameter in the pore volume obtained by the pore distribution measurement were regarded as the most frequent pores.
The ratio of the area of pores having a diameter of at most 0.1 μm to the accumulation of the pore area obtained by the pore distribution measurement was obtained and taken as the pore area ratio of pores of at most 10 μm. The pore area ratio of pores having a diameter of at most 0.05 μm was similarly obtained. Further, as a pretreatment for the pore distribution measurement, the sample was dried by being left at rest at 100° C.
Pure water at 80° C. was stirred while the air was blown thereinto. A 2 mol/L manganese sulfate aqueous solution and a 0.25 mol/L sodium hydroxide aqueous solution were respectively added to the pure water so that the oxidation-reduction potential of the pure water would be constant at 100 mV, whereby manganese oxide was precipitated to obtain a slurry (hereinafter referred to as “mixed reaction slurry”).
The manganese sulfate aqueous solution and the sodium hydroxide aqueous solution were continuously added to the mixed reaction slurry so that OH−/Mn2+ (mol/mol) of the sodium hydroxide aqueous solution and the manganese sulfate aqueous solution added (hereinafter referred to as “manganese molar ratio”) would be 0.46.
After the manganese oxide was precipitated, the rate of withdrawal of the mixed reaction slurry was adjusted, and reaction was carried out for 8 hours while the solid content concentration of trimanganese tetraoxide in the mixed reaction slurry was adjusted to be 0.95 wt %.
After the reaction, the mixed reaction slurry was recovered, subjected to filtration, washed and dried to obtain manganese oxide.
The X-ray diffraction pattern of the obtained manganese oxide was the same pattern as No. 24734 X-ray diffraction pattern of the JCPDS pattern, and its crystal phase was a spinel structure. Further, the degree of oxidation of manganese of the manganese oxide as represented as MnOx was x=1.34. From these results, the obtained manganese oxide was confirmed to be a trimanganese tetraoxide single phase.
The results of evaluation of the trimanganese tetraoxide particles in Example 1 are shown in Table 1.
Further, of the obtained trimanganese tetraoxide particles, the density by the measurement method in accordance with JIS R1628 (hereinafter referred to as “JIS density”) was measured. As a result, the JIS density of the trimanganese tetraoxide in Example 1 was 1.54 g/cm3, which was 1.1 times the tap density.
Manganese oxide was obtained in the same manner as in Example 1 except that the reaction time was 1.5 hours.
The X-ray diffraction pattern of the obtained manganese oxide was the same pattern as No. 24734 X-ray diffraction pattern of the JCPDS pattern, and its crystal phase was a spinel structure. Further, the degree of oxidation of manganese of the manganese oxide as represented as MnOx was x=1.35. From these results, the obtained manganese oxide was confirmed to be a trimanganese tetraoxide single phase.
The results of evaluation of the trimanganese tetraoxide particles in Example 2 are shown in Table 1.
Manganese oxide was obtained in the same manner as in Example 1 except that the concentration of the manganese sulfate aqueous solution was 0.2 mol/L, and the reaction time was 9 hours.
The X-ray diffraction pattern of the obtained manganese oxide was the same pattern as No. 24734 X-ray diffraction pattern of the JCPDS pattern, and its crystal phase was a spinel structure. Further, the degree of oxidation of manganese of the manganese oxide as represented as MnOx was x=1.34. From these results, the obtained manganese oxide was confirmed to be a trimanganese tetraoxide single phase.
The results of evaluation of the trimanganese tetraoxide particles in Example 3 are shown in Table 1.
Manganese oxide was obtained in the same manner as in Example 1 except that the concentration of the manganese sulfate aqueous solution was 0.2 mol/L, the solid content concentration of trimanganese tetraoxide in the mixed reaction slurry was 0.56 wt %, and the reaction time was 30 minutes.
The X-ray diffraction pattern of the obtained manganese oxide was the same pattern as No. 24734 X-ray diffraction pattern of the JCPDS pattern, and its crystal phase was a spinel structure. Further, the degree of oxidation of manganese of the manganese oxide as represented as MnOx was x=1.34. From these results, the obtained manganese oxide was confirmed to be a trimanganese tetraoxide single phase.
The results of evaluation of the trimanganese tetraoxide particles in Example 4 are shown in Table 1.
Manganese oxide was obtained in the same manner as in Example 1 except that after manganese oxide was precipitated, the rate of withdrawal of the mixed reaction slurry was adjusted and the reaction was carried out for 48 hours while the solid content concentration of trimanganese tetraoxide in the mixed reaction slurry was adjusted to be 5.46 wt %.
The X-ray diffraction pattern of the obtained manganese oxide was the same pattern as No. 24734 X-ray diffraction pattern of the JCPDS pattern, and its crystal phase was a spinel structure. Further, the degree of oxidation of manganese of the manganese oxide as represented as MnOx was x=1.34. From these results, the obtained manganese oxide was confirmed to be a trimanganese tetraoxide single phase.
The trimanganese tetraoxide in Comparative Example 1 had a high fillability with a tap density of 2.2 g/cm3, but the average primary particle size was large, and the pore volume was small.
The results of evaluation of the trimanganese tetraoxide particles in Comparative Example 1 are shown in Table 1.
| TABLE 1 | ||||||
| Comp. | ||||||
| Ex. 1 | Ex. 2 | Ex. 3 | Ex. 4 | Ex. 1 | ||
| Average primary particle size (μm) | 0.44 | 0.31 | 0.38 | 0.38 | 0.35 |
| Pore volume (mL/g) | 0.50 | 0.98 | 0.56 | 1.23 | 0.30 |
| Pore volume ratio (%) of |
9 | 15 | 15 | 15 | 10 |
| having diameter of at least 10 μm | |||||
| Pore volume ratio (%) of pores | 29 | 36 | 34 | 33 | 24 |
| having diameter of at most 2 μm | |||||
| Pore area ratio (%) of pores having | 9 | 8 | 11 | 8 | 1.2 |
| diameter of at most 0.1 μm | |||||
| Diameter (μm) of most frequent | 3.8 | 3.0 | 2.9 | 3.0 | 3.0 |
| pores | |||||
| Modal particle size (μm) | 15.6 | 13.1 | 13.1 | 9.3 | 8.5 |
| Average particle size (μm) | 11.7 | 11.0 | 12.2 | 5.5 | 8.6 |
| Tap density (g/cm3) | 1.4 | 0.9 | 1.3 | 0.8 | 1.8 |
| BET specific surface area (m2/g) | 4 | 6 | 5.8 | 13 | 1.5 |
| SO4 (wt %) | 0.31 | 0.36 | 0.35 | 0.24 | 0.60 |
| Ca (wtppm) | 32 | 38 | 24 | 55 | 80 |
| Mg (wtppm) | 13 | 14 | 12 | 14 | 50 |
Trimanganese tetraoxide of the present invention is excellent in the handleability and is suitably used as a manganese material of a lithium manganese oxide which is industrially easily handled.
The entire disclosure of Japanese Patent Application No. 2012-096297 filed on Apr. 20, 2012 including specification, claims, drawings and summary is incorporated herein by reference in its entirety.
Claims (13)
1. Trimanganese tetraoxide particles comprising trimanganese tetraoxide primary particles which have an average primary particle size of at most 2 μm and which are agglomerated, the pore volume of pores being at least 0.5 mL/g,
wherein the pore volume ratio of pores having a diameter of at least 10 μm as measured by a mercury intrusion technique is at most 20%.
2. The trimanganese tetraoxide particles according to claim 1 , wherein the most frequent pores are pores having a diameter of at most 5 μm.
3. The trimanganese tetraoxide particles according to claim 1 , wherein the average particle size is at least 5 μm and at most 50 μm.
4. The trimanganese tetraoxide particles according to claim 1 , wherein the modal particle size is larger than the average particle size.
5. The trimanganese tetraoxide particles according to claim 1 , wherein the content of sulfate radicals is at most 0.5 wt %.
6. The trimanganese tetraoxide particles according to claim 1 , wherein the average primary particle size is at least 0.2 μm and at most 0.5 μm.
7. The trimanganese tetraoxide particles according to claim 1 , wherein the pore volume of pores is at most 2 mL/g.
8. A process for producing the trimanganese tetraoxide particles as defined in claim 1 , which comprises a crystallization step of directly crystallizing trimanganese tetraoxide from a manganese salt aqueous solution, wherein in the crystallization step, the manganese salt aqueous solution and an alkali aqueous solution are mixed so that the oxidation-reduction potential is at least 0 mV and OH−/Mn2+ (mol/mol) is at most 0.55, to obtain a slurry, and the solid content concentration of the slurry is adjusted to be at most 2 wt %.
9. The production process according to claim 8 , wherein the oxidation-reduction potential is at least 60 mV and at most 200 mV.
10. The production process according to claim 8 , wherein in the crystallization step, the slurry having a solid content concentration of at most 2 wt % is aged for at least 10 minutes.
11. The production process according to claim 8 , wherein the temperature of the manganese salt aqueous solution is at least 60° C. and at most 95° C.
12. The production process according to claim 8 , wherein OH−/Mn2+ (mol/mol) is at least 0.35.
13. A process for producing a lithium oxide, which comprises a mixing step of mixing the trimanganese tetraoxide particles as defined in claim 1 with a lithium compound, and a heating step of subjecting the mixture to heat treatment.
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| PCT/JP2013/061425 WO2013157587A1 (en) | 2012-04-20 | 2013-04-17 | Manganese(iii, iv) oxide and method for producing same |
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| JP5966719B2 (en) * | 2012-07-23 | 2016-08-10 | 東ソー株式会社 | Method for producing trimanganese tetraoxide |
| JP6015320B2 (en) | 2012-10-03 | 2016-10-26 | 東ソー株式会社 | Trimanganese tetraoxide and method for producing the same |
| JP6578682B2 (en) * | 2015-03-12 | 2019-09-25 | 東ソー株式会社 | Trimanganese tetraoxide and method for producing the same |
| CN110776018B (en) * | 2019-10-29 | 2022-02-01 | 湖南中伟新能源科技有限公司 | Cobalt oxyhydroxide, preparation method thereof, lithium cobaltate, electrode and lithium ion battery |
| CN114180632A (en) * | 2022-01-18 | 2022-03-15 | 西安理工大学 | Method for rapidly preparing porous trimanganese tetroxide nano material with large specific surface area in one step |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001093527A (en) | 1999-09-22 | 2001-04-06 | Matsushita Electric Ind Co Ltd | Positive electrode activating material for nonaqueous electrolytic secondary battery and its manufacturing method |
| JP2001261343A (en) | 2000-03-17 | 2001-09-26 | Unitika Ltd | Super fine particle of trimanganese tetraoxide and method of producing the same |
| JP2001354425A (en) | 2000-06-12 | 2001-12-25 | Tanaka Chemical Corp | Manganese tetratrioxide and method for manufacturing the same |
| JP2003086180A (en) | 2001-09-11 | 2003-03-20 | Masayuki Yoshio | Positive electrode active material of nonaqueous electrolyte secondary battery and secondary battery using it |
| JP2003272629A (en) | 2002-03-19 | 2003-09-26 | Toda Kogyo Corp | Positive electrode active material for nonaqueous electrolyte secondary battery and its manufacturing method |
| JP2004292264A (en) | 2003-03-27 | 2004-10-21 | Toda Kogyo Corp | Trimanganese tetroxide particle, its production method, nonaqueous electrolyte secondary battery, positive electrode active substance therefor and its preparation method |
| WO2005019109A1 (en) | 2003-08-26 | 2005-03-03 | Matsushita Electric Industrial Co., Ltd. | Method for producing manganese oxide nanostructure and oxygen reduction electrode using such manganese oxide nanostructure |
| US20060017456A1 (en) | 2002-10-23 | 2006-01-26 | Renesas Technology Corp. | Semiconductor device with bus terminating function |
| JP2012023015A (en) | 2010-01-08 | 2012-02-02 | Mitsubishi Chemicals Corp | Cathode material powder for lithium secondary battery and manufacturing method thereof and cathode for lithium secondary cattery and lithium secondary battery |
| WO2012046735A1 (en) | 2010-10-06 | 2012-04-12 | 東ソー株式会社 | Manganese oxide and method for producing same, and method for producing lithium manganese composite oxide using same |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63215521A (en) * | 1987-03-02 | 1988-09-08 | Mitsui Mining & Smelting Co Ltd | Production of trimanganese tetroxide |
| JP3272759B2 (en) * | 1992-01-28 | 2002-04-08 | 関西熱化学株式会社 | Manufacture of trimanganese oxide |
| JP3146359B2 (en) * | 1999-08-04 | 2001-03-12 | 工業技術院長 | Ultrafine manganese oxide powder and method for producing the same |
| US6929883B2 (en) * | 2000-05-30 | 2005-08-16 | Seimi Chemical Co., Ltd. | Lithium-transition metal composite oxide |
| CN101146746A (en) * | 2005-09-28 | 2008-03-19 | Agc清美化学股份有限公司 | Process for producing lithium-containing composite oxide |
| CN100554165C (en) * | 2007-12-14 | 2009-10-28 | 北京科技大学 | A kind of method of trimanganese tetroxide preparation |
| JP2010120842A (en) * | 2008-10-24 | 2010-06-03 | Soshin Kagaku Sangyo Kk | Method for producing tri-metal tetraoxide |
| KR101051313B1 (en) * | 2009-07-27 | 2011-07-22 | 주식회사 쓰리지테크놀러지 | Opening prevention device of window opener |
| CN101898796A (en) * | 2010-08-04 | 2010-12-01 | 湖南汇通科技有限责任公司 | High-proportion manganous-manganic oxide and preparation method thereof |
| CN102303910B (en) * | 2011-07-26 | 2014-06-25 | 陕西师范大学 | Method for preparing uniform-spherical trimanganese tetroxide |
-
2013
- 2013-04-15 JP JP2013084916A patent/JP6194618B2/en active Active
- 2013-04-17 CN CN201380020721.2A patent/CN104245592B/en active Active
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- 2013-04-17 WO PCT/JP2013/061425 patent/WO2013157587A1/en active Application Filing
- 2013-04-17 KR KR1020147027857A patent/KR102005601B1/en active IP Right Grant
- 2013-04-17 EP EP13777948.4A patent/EP2840068B1/en active Active
- 2013-04-17 TW TW102113564A patent/TWI596062B/en active
- 2013-04-17 ES ES13777948.4T patent/ES2681976T3/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001093527A (en) | 1999-09-22 | 2001-04-06 | Matsushita Electric Ind Co Ltd | Positive electrode activating material for nonaqueous electrolytic secondary battery and its manufacturing method |
| JP2001261343A (en) | 2000-03-17 | 2001-09-26 | Unitika Ltd | Super fine particle of trimanganese tetraoxide and method of producing the same |
| JP2001354425A (en) | 2000-06-12 | 2001-12-25 | Tanaka Chemical Corp | Manganese tetratrioxide and method for manufacturing the same |
| JP2003086180A (en) | 2001-09-11 | 2003-03-20 | Masayuki Yoshio | Positive electrode active material of nonaqueous electrolyte secondary battery and secondary battery using it |
| JP2003272629A (en) | 2002-03-19 | 2003-09-26 | Toda Kogyo Corp | Positive electrode active material for nonaqueous electrolyte secondary battery and its manufacturing method |
| US20060022703A1 (en) | 2002-10-23 | 2006-02-02 | Renesas Technology Corp. | Semiconductor device with bus terminating function |
| US20060017456A1 (en) | 2002-10-23 | 2006-01-26 | Renesas Technology Corp. | Semiconductor device with bus terminating function |
| US20070103190A1 (en) | 2002-10-23 | 2007-05-10 | Renesas Technology Corp. | Semiconductor device with bus terminating function |
| JP2004292264A (en) | 2003-03-27 | 2004-10-21 | Toda Kogyo Corp | Trimanganese tetroxide particle, its production method, nonaqueous electrolyte secondary battery, positive electrode active substance therefor and its preparation method |
| WO2005019109A1 (en) | 2003-08-26 | 2005-03-03 | Matsushita Electric Industrial Co., Ltd. | Method for producing manganese oxide nanostructure and oxygen reduction electrode using such manganese oxide nanostructure |
| US20060018821A1 (en) | 2003-08-26 | 2006-01-26 | Matsushita Electric Industrial Co., Ltd. | Method for manufacturing manganese oxide nanostructure and oxygen reduction electrode using said manganese oxide nanostructure |
| JP2012023015A (en) | 2010-01-08 | 2012-02-02 | Mitsubishi Chemicals Corp | Cathode material powder for lithium secondary battery and manufacturing method thereof and cathode for lithium secondary cattery and lithium secondary battery |
| WO2012046735A1 (en) | 2010-10-06 | 2012-04-12 | 東ソー株式会社 | Manganese oxide and method for producing same, and method for producing lithium manganese composite oxide using same |
| US20130187083A1 (en) | 2010-10-06 | 2013-07-25 | Tosoh Corporation | Manganese oxide and method for producing same, and method for producing lithium manganese composite oxide using same |
| US9150427B2 (en) * | 2010-10-06 | 2015-10-06 | Tosoh Corporation | Manganese oxide and method for producing same, and method for producing lithium manganese composite oxide using same |
Non-Patent Citations (7)
| Title |
|---|
| J. Pattanayak et al., "Preparation and Thermal Stability of Manganese Oxides Obtained by Precipitation from Aqueous Manganese Sulphate Solution", Thermochim Acta, Nov. 1, 1989, pp. 193-204, vol. 153. |
| Lee et al., "Designing tunable microstructures of Mn3O4 nanoparticles by using surfactant-assisted dispersion," Journal of Power Sources 206 (2012) 469-475. Available online Jan. 28, 2012. * |
| S. Ardizzone et al., "Mn304 and y-MnOOH powders, preparation phase composition and XPS characterisation", Colloids and Surfaces A: Physicochemical and Engineering Aspects, Mar. 31, 1998, pp. 305-312, vol. 134. |
| Search report from PCT/JP2013/061425, mail date is Jul. 16, 2013. |
| T. Ozkaya et al., "A novel synthetic route to Mn3O4 nanoparticales and their magnetic evaluation", Physica B: Condensed Matter, Oct. 1, 2008, pp. 3760-3764, vol. 403, No. 19-20. |
| U.S. Appl. No. 14/386,480 to Takahiro Matsunaga et al., filed Sep. 19, 2014. |
| Z.Zhang et al., "Effect of Hyrothermal Time, pH and Alkali on Crystal Phase and Morphology of Manganese Oxides", Journal of Dispersion Science and Technology, 2007, pp. 793-796, vol. 28, No. 5. |
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